WO2015054346A1 - Reverse photochromic borosilicate glasses - Google Patents

Reverse photochromic borosilicate glasses Download PDF

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Publication number
WO2015054346A1
WO2015054346A1 PCT/US2014/059623 US2014059623W WO2015054346A1 WO 2015054346 A1 WO2015054346 A1 WO 2015054346A1 US 2014059623 W US2014059623 W US 2014059623W WO 2015054346 A1 WO2015054346 A1 WO 2015054346A1
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WIPO (PCT)
Prior art keywords
glass composition
borosilicate glass
photochromic borosilicate
photochromic
color
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Application number
PCT/US2014/059623
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English (en)
French (fr)
Inventor
John Christopher Mauro
Lynn Marie Thirion
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Corning Incorporated
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Application filed by Corning Incorporated filed Critical Corning Incorporated
Priority to CN201480067314.1A priority Critical patent/CN105813998B/zh
Priority to JP2016521713A priority patent/JP6463350B2/ja
Priority to KR1020167011690A priority patent/KR102271837B1/ko
Priority to EP18188056.8A priority patent/EP3424888B1/en
Priority to EP14786760.0A priority patent/EP3055260B1/en
Publication of WO2015054346A1 publication Critical patent/WO2015054346A1/en

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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/11Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/02Surface treatment of glass, not in the form of fibres or filaments, by coating with glass
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/002Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C23/00Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/0005Other surface treatment of glass not in the form of fibres or filaments by irradiation
    • C03C23/002Other surface treatment of glass not in the form of fibres or filaments by irradiation by ultraviolet light
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00Compositions for glass with special properties
    • C03C4/04Compositions for glass with special properties for photosensitive glass
    • C03C4/06Compositions for glass with special properties for photosensitive glass for phototropic or photochromic glass
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02Frit compositions, i.e. in a powdered or comminuted form
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/06Frit compositions, i.e. in a powdered or comminuted form containing halogen
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2204/00Glasses, glazes or enamels with special properties
    • C03C2204/04Opaque glass, glaze or enamel
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2207/00Compositions specially applicable for the manufacture of vitreous enamels
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00Methods for coating glass
    • C03C2218/10Deposition methods
    • C03C2218/15Deposition methods from the vapour phase
    • C03C2218/152Deposition methods from the vapour phase by cvd
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00Technologies relating to the processing of minerals
    • Y02P40/50Glass production, e.g. reusing waste heat during processing or shaping

Definitions

  • the present disclosure relates to borosilicate glasses that display reverse photochromic and thermally darkenable behavior.
  • the disclosure also relates to articles made from such borosilicate glasses, precursor glasses for such borosilicate glasses, and methods for obtaining such borosilicate glasses and related articles.
  • Typical photochromic glasses darken in response to ultraviolet (UV) irradiation and revert to a colorless or near colorless thermally stable state when UV irradiation ceases.
  • UV ultraviolet
  • Such typical photochromic glasses are commonly formed of borosilicate.
  • "reverse" photochromic glasses have heretofore been composed of silica-free, alkali-free lanthanum borate.
  • Such borate glasses are highly hygroscopic and ill- suited for applications in which moisture is or may be present.
  • borate glasses typically have lower thermal stability and chemical durability than borosilicate glasses and require expensive, heavy rare earth elements.
  • such glasses cannot be strengthened by ion-exchange processes.
  • compositions disclosed herein provide borosilicate glasses exhibiting reverse photochromic properties.
  • such borosilicate glasses may retain their reverse photochromic properties even after ion-exchange strengthening treatment.
  • borosilicate glasses may be thermally darkenable.
  • Thermally darkenable means the optical density of the darkened state increases with increased temperature. In some embodiments, at higher temperatures, the glass may remain dark in spite of relatively intense bleaching light.
  • borosilicate glasses that display reverse photochromic and thermally darkenable behavior.
  • the glasses may be chemically strengthened via an ion exchange process.
  • the reverse photochromic, thermally darkenable glasses may be used as one or more layers of a multi-layer glass laminate.
  • a photochromic borosilicate glass composition having (in weight %) 66-76% Si0 2 , 0-8% A1 2 0 3 , 10-18% B 2 0 3 , 0-4% Li 2 0, 0-12% Na 2 0, 0-12% K 2 0, 1-1.5% Ag, 1.5-2.5% CI " and 0.01-0.06% of a summed amount of CuO and NiO, wherein the glass composition is bleachable upon exposure to ultraviolet irradiation from a stable state color or shade to a lighter color or shade.
  • Such photochromic borosilicate glass composition may be thermally darkenable.
  • the composition may be thermally darkenable at a temperature of 150°C or greater.
  • the aforementioned photochromic borosilicate glass composition includes 2-12% Na 2 0.
  • a photochromic borosilicate glass composition having (in weight %) 66-76% Si0 2 , 0-8% A1 2 0 3 , 10-18% B 2 0 3 , 0-12% Na 2 0, 0-12% K 2 0, 1-1.5% Ag, 1.5-2.5% CI " and 0.01-0.06% of a summed amount of CuO and NiO, wherein the glass composition is bleachable upon exposure to ultraviolet irradiation from a stable state color or shade to a lighter color or shade and is substantially free of Li 2 0.
  • a photochromic borosilicate glass composition having (in weight %) 66-76% Si0 2 , 0-8% A1 2 0 3 , 10-18% B 2 0 3 , 0-4% Li 2 0, 0-12% Na 2 0, 0-12% K 2 0, 1-1.5% Ag, 1.5-2.5% CI " and 0.01-0.06% of a summed amount of CuO and NiO, wherein the glass composition is bleachable upon exposure to ultraviolet irradiation from a stable state color or shade to a lighter color or shade and is substantially free of Br " .
  • photochromic borosilicate glass compositions may include 2-8% A1 2 0 3 , 4-12% Na 2 0 and 0-6% K 2 0, wherein the weight % of Na 2 0 is greater than the weight % of K 2 0.
  • the glass composition may be substantially free of Li 2 0 and/or Br " .
  • a photochromic borosilicate glass composition includes 68.6-71.6% Si0 2 , 3-6% A1 2 0 3 , 13.4% B 2 0 3 , 4.5-9% Na 2 0, 0-4.5% K 2 0, 1.2% Ag, 1.8% CI " and 0.03% CuO, wherein the weight % of Na 2 0 is greater than the weight % of K 2 0 and the composition is substantially free of Li 2 0 and Br " .
  • immersion of the photochromic borosilicate glass compositions disclosed herein in a molten salt bath for a predetermined time and temperature causes ion-exchange.
  • a photochromic borosilicate glass composition which when exposed to ultraviolet irradiation exhibits a lightening in color or shade and is thermally darkenable, the photochromic borosilicate glass composition including (in weight %) 66-76% Si0 2 , 2-8% A1 2 0 3 , 10-18% B 2 0 3 , 0-4% Li 2 0, 2-12% Na 2 0, 0- 12% K 2 0, 1-1.5% Ag, 1.5-2.5% CI " and 0.01-0.06% of a summed amount of CuO and NiO, wherein the photochromic borosilicate glass composition is substantially free of Br " .
  • the foregoing glass composition includes 1.2% Ag and 1.8% CI " .
  • a photochromic borosilicate glass composition which when exposed to ultraviolet irradiation exhibits a lightening in color or shade and is thermally darkenable, the photochromic borosilicate glass composition including (in weight %) 66-76% Si0 2 , 2-8% A1 2 0 3 , 13.4% B 2 0 3 , 0-4% Li 2 0, 2-12% Na 2 0, 0-12% K 2 0, 1- 1.5% Ag, 1.5-2.5% CI " and 0.01-0.06% of a summed amount of CuO and NiO, wherein the photochromic borosilicate glass composition is substantially free of Br " .
  • a photochromic borosilicate glass composition which when exposed to ultraviolet irradiation exhibits a lightening in color or shade and is thermally darkenable, the photochromic borosilicate glass composition including (in weight %) 66-76% Si0 2 , 2-8% A1 2 0 3 , 10-18% B 2 0 3 , 2-12% Na 2 0, 0-12% K 2 0, 1-1.5% Ag, 1.5- 2.5% CI " and 0.01-0.06% of a summed amount of CuO and NiO, wherein the photochromic borosilicate glass composition is substantially free of Br " and Li 2 0.
  • a photochromic borosilicate glass composition which when exposed to ultraviolet irradiation exhibits a lightening in color or shade and is thermally darkenable, the photochromic borosilicate glass composition including (in weight %) 66-76% Si0 2 , 6% A1 2 0 3 , 13.4% B 2 0 3 , 0-4% Li 2 0, 4.5% Na 2 0, 0-12% K 2 0, 1.2% Ag, 1.8% CI " , 0.03% CuO and 0.03-0.06% of a summed amount of CuO and NiO, wherein the photochromic borosilicate glass composition is substantially free of Br " .
  • a photochromic borosilicate glass composition which when exposed to ultraviolet irradiation exhibits a lightening in color or shade and is thermally darkenable, the photochromic borosilicate glass composition including (in weight %) 66-76% Si0 2 , 6% A1 2 0 3 , 13.4% B 2 0 3 , 0-4% Li 2 0, 9% Na 2 0, 1.2% Ag, 1.85% CI " , 0.03% CuO and 0.03-0.06% of a summed amount of CuO and NiO, wherein the photochromic borosilicate glass composition is substantially free of Br " and K 2 0.
  • a photochromic borosilicate glass composition which when exposed to ultraviolet irradiation exhibits a lightening in color or shade and is thermally darkenable, the photochromic borosilicate glass composition including (in weight %) 66-76% Si0 2 , 3% A1 2 0 3 , 13.4% B 2 0 3 , 0-4% Li 2 0, 6% Na 2 0, 3% K 2 0, 1.2% Ag, 1.8% CI " , 0.03% CuO and 0.03-0.06% of a summed amount of CuO and NiO, wherein the photochromic borosilicate glass composition is substantially free of Br " .
  • a method of strengthening a glass composition includes immersing in a molten salt bath a photochromic borosilicate glass composition having (in weight %) 66-76% Si0 2 , 2-8% A1 2 0 3 , 10-18% B 2 0 3 , 0-4% Li 2 0, 2-12% Na 2 0, 0-12% K 2 0, 1-1.5% Ag, 1.5-2.5% CI " and 0.01-0.06% of a summed amount of CuO and NiO, wherein the photochromic borosilicate glass composition is substantially free of Br " , and wherein the photochromic borosilicate glass composition is immersed in the molten salt bath for a time and at a temperature sufficient to cause ion-exchange.
  • the temperature of the bath may be between about 350°C and 450°C and the predetermined period of time may be between about 6 and 10 hours.
  • the molten salt bath includes KNO 3
  • a substrate such as a glass substrate
  • a layer to the substrate.
  • the advantageous functional properties achieved by adding a layer to a substrate are numerous, one such functional property is photo chromicity.
  • one or more aspects may involve providing a reverse photochromic borosilicate glass layer on a substrate such as another glass.
  • an oxide glass such as Gorilla® Glass, which is available from Corning Incorporated, has been widely used in consumer electronics products. Such glass is used in applications where the strength of conventional glass is insufficient to achieve desired performance levels.
  • Gorilla ® Glass is manufactured by chemical strengthening (ion exchange) in order to achieve high levels of strength while maintaining desirable optical characteristics (such as high transmission, low reflectivity, and suitable refractive index).
  • Strengthened glass through ion exchange (IX) techniques can produce high levels of compressive stress in the treated glass, as high as about 400 to 1000 MPa at the surface.
  • One or more layers of borosilicate reverse photochromic glass may be applied to a substrate such as Gorilla ® Glass to provide a device having reverse photochromic properties.
  • FIG. 1 is a photographic view of images of glasses before and after 15 minutes of exposure to high intensity LED white light (*616GB is after exposure only);
  • FIG. 2 is a photographic view of images of a further batch of glasses before and after 15 minutes of exposure to high intensity LED white light;
  • FIG. 3 is a photographic view of images of additional glasses before and after 15 minutes of exposure to high intensity LED white light;
  • FIG. 4 is a graphical representation of a L*a*b* color scale employed in connection with establishing color coordinates of photochromic glasses made in accordance with the present disclosure
  • FIG. 5 is a photographic view of images of glasses before and after ion exchange (IX) in refined KNO 3 (370°C/8 hours); all images are before exposure to the white LED light;
  • FIG. 6 is a photographic view of images of glasses subjected to ion exchange (IX) processes, including images of glass samples prior to exposure to LED light and the same samples after 15 minutes of exposure to LED light;
  • IX ion exchange
  • FIG. 7 is a schematic view of a glass substrate with a layer of material.
  • FIG. 8 is a schematic, side view of the glass substrate of FIG. 7 taken through cross-sectional line 2-2.
  • Photochromic borosilicate glass compositions having (in weight %) 66-76% Si0 2 , 0-8% A1 2 0 3 , 10-18% B 2 0 3 , 0-4% Li 2 0, 0-12% Na 2 0, 0-12% K 2 0, 1-1.5% Ag, 1.5-2.5%) CI " and 0.01-0.06%) of a summed amount of CuO and NiO, wherein the glass composition is bleachable upon exposure to ultraviolet irradiation from a stable state color or shade to a lighter color or shade.
  • Such photochromic borosilicate glass compositions may be thermally darkenable.
  • the composition may be thermally darkenable at a temperature of 150°C or greater.
  • such borosilicate glasses retain their reverse photochromic properties even after ion-exchange strengthening treatment.
  • such ion-exchange strengthened borosilicate glasses may be thermally darkenable.
  • compositions disclosed herein are substantially free of Br " .
  • compositions disclosed herein are substantially free of [ 0046]
  • Tables 1-3 and corresponding FIGs. 1-3 were tested for reverse photochromic properties and thermal darkening properties according to the following methods.
  • sample 616HD to be thermally darkenable, i.e., exposure to heat changed the exposed glass back to its original color state.
  • IX Ion exchange
  • Corning Gorilla® Glass available from Corning Incorporated.
  • Ion exchange is carried out by immersion of a glass sheet into a molten salt bath for a predetermined period of time, where ions within the glass sheet at or near the surface thereof are exchanged for larger metal ions, for example, from the salt bath.
  • the molten salt bath may include KNO 3
  • the temperature of the molten salt bath may within the range of about 400 - 500 °C
  • the predetermined time period may be within the range of about 2-24 hours, and more specifically between about 2-10 hours.
  • the incorporation of the larger ions into the glass strengthens the sheet by creating a compressive stress in a near surface region. A corresponding tensile stress is induced within a central region of the glass sheet to balance the compressive stress.
  • Sodium ions within the glass sheet may be replaced by potassium ions from the molten salt bath, though other alkali metal ions having a larger atomic radius, such as rubidium or cesium, may replace smaller alkali metal ions in the glass. According to particular embodiments, alkali metal ions in the glass sheet may be replaced by Ag+ ions. Similarly, other alkali metal salts such as, but not limited to, sulfates, halides, and the like may be used in the ion exchange process.
  • Ion-exchangeable glasses that are suitable for use in the embodiments herein include borosilicate glasses.
  • "ion exchangeable” means that a glass is capable of exchanging cations located at or near the surface of the glass with cations of the same valence that are either larger or smaller in size.
  • Borosilicate glasses having reverse photochromic properties which may be chemically strengthened in a potassium salt bath disclosed herein include the following range of compositions (mol %): 66-76 Si0 2 , 2-8 A1 2 0 3 , 10-18 B 2 0 3 , 0-4 Li 2 0, 4-12 Na 2 0, 0-6 K 2 0, 1-1.5 Ag, 1.5-2.5 CI " , wherein Na 2 0 > K 2 0 and the summed amount of CuO and NiO is 0.01-0.06.
  • a nonzero level of [A1 2 0 3 ] is desired since alumina is a key enabler of effective ion exchange in terms of both ion mobility and obtaining the desired level of compressive stress. Also, the concentration of Na 2 0 in the composition should be sufficiently high relative to K 2 0 to enable strengthening.
  • FIG. 5 depicts samples in their pre-ion exchange state and their post-ion exchange state (labeled "IX"). It is noted that ion exchange also contributed to some degree of color change on at least some of the sample glasses as seen in FIG. 5.
  • IX ion exchanged
  • Table 8 provides FSM data for samples subjected to ion exchange treatment for 8 hours at 370°C with refined KNO 3 . Stress measurements were taken using an Orihara FSM- 6000LE measurement instrument on all the ion-exchange strengthened samples. Only three glass sample compositions (those having sufficiently high [Na 2 0]) had enough modes for recordable data, six glass samples having one mode and two samples having no visible modes.
  • a structure 100 may include a substrate 102 of interest in connection with the development of novel processes and structures to improve the photochromic properties of the substrate 102.
  • the substrate 102 material may be glass, specifically Gorilla® Glass from Corning Incorporated, which is an ion-exchange glass, usually an alkali alumino silicate glass or alkali aluminoboro silicate glass.
  • Gorilla® Glass from Corning Incorporated
  • the specific substrate material is not limited to glass, or Gorilla® Glass in particular, however, such material was selected for experimentation and example.
  • a reverse photochromic layer on the substrate 102 may provide reverse photochromic properties to the structure 100.
  • the structure 100 includes the substrate 102 having first surface (not shown) and second, opposing surface 106, and at least one reverse photochromic borosilicate glass layer 104 substantially covering the substrate 102.
  • substantially covering herein means that the superior layer (i.e., the layer 104) overlies the inferior layer (i.e., the substrate 102) either directly or indirectly through one or more intermediate layers.
  • the layer 104 may be disposed on either or both sides of the substrate 102. In the embodiment illustrated in FIG. 8, there are no intermediate layers shown between, for example, the layer 104 and the substrate 102, although such intermediate layers are contemplated.
  • the reverse photochromic borosilicate glass layer 104 may be formed via a single layer of material.
  • the reverse photochromic borosilicate glass layer 104 may be strengthened by ion-exchange processes disclosed herein. Those skilled in the art will appreciate from the disclosure herein that the details presented will readily enable a skilled artisan to employ one or more methodologies for applying layer 104 by applying well-known layering techniques.
  • the substrate 102 is substantially planar, although other embodiments may employ a curved or otherwise shaped or sculpted substrate 102. Additionally or alternatively, the thickness of the substrate 102 may vary, for aesthetic and/or functional reasons, such as employing a higher thickness at edges of the substrate 102 as compared with more central regions.
  • the substrate 102 may be formed of any suitable material, such as from at least one of quartz, glass, glass-ceramic, oxide glass, ion exchanged glass, polymer, combinations thereof, or other material(s).
  • any suitable glass composition may be employed, such as soda lime glass (Si0 2 , Na 2 0, CaO, etc.), metallic alloy glasses, ionic melt glass, polymer glasses (acrylic glass, polycarbonate, polyethylene terephthalate), etc.
  • ALD atomic layer deposition
  • ALD atomic layer deposition
  • semiconductor processing has been one of the main applications for the recent developments in ALD processing, the conformality capabilities achieved by ALD on high aspect structures has applicability to the instant application. Indeed, most ALD processes are based on binary reaction sequences where two surface reactions occur and deposit a binary compound film. As there are only a finite number of surface sites, the reactions are limited to depositing a finite number of surface species.
  • the two reactions may proceed in a sequential fashion to deposit a thin film with atomic level control.
  • the advantages of the ALD process include: (i) precise thickness control at the Angstrom or monolayer level; and (ii) excellent step coverage and conformal deposition on high aspect ratio structures.
  • the layer 104 is relatively thin, e.g., the layer 104 will generally have a thickness within some range.
  • contemplated thickness ranges include at least one of: (i) between about 10 - 200 nm; (ii) between about 20 - 100 nm; and (iii) between about 30 - 90 nm. Such ranges may be suited for a particular functional property, for example, the application of a layer 104 for thin film transistor applications, sensor applications, and display device applications such as monitor and telecommunication device applications.
  • Still further contemplated thickness ranges include at least one of: (i) between about 50 - 10,000 nm; (ii) between about 500 - 10,000 nm; and (iii) between about 1000 - 2000 nm.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Toxicology (AREA)
  • Health & Medical Sciences (AREA)
  • Glass Compositions (AREA)
  • Optical Filters (AREA)
  • Surface Treatment Of Glass (AREA)
PCT/US2014/059623 2013-10-09 2014-10-08 Reverse photochromic borosilicate glasses WO2015054346A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN201480067314.1A CN105813998B (zh) 2013-10-09 2014-10-08 反向光致变色硼硅酸盐玻璃
JP2016521713A JP6463350B2 (ja) 2013-10-09 2014-10-08 逆フォトクロミックホウケイ酸ガラス
KR1020167011690A KR102271837B1 (ko) 2013-10-09 2014-10-08 역 광색성 보로실리케이트 유리
EP18188056.8A EP3424888B1 (en) 2013-10-09 2014-10-08 Reverse photocromic borosilicate glasses
EP14786760.0A EP3055260B1 (en) 2013-10-09 2014-10-08 Reverse photochromic borosilicate glasses

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TWI647199B (zh) 2019-01-11
EP3055260A1 (en) 2016-08-17
JP2016535715A (ja) 2016-11-17
EP3424888A1 (en) 2019-01-09
US10487003B2 (en) 2019-11-26
JP6463350B2 (ja) 2019-01-30
EP3424888B1 (en) 2019-11-27
US9527769B2 (en) 2016-12-27
EP3055260B1 (en) 2018-09-26
CN105813998B (zh) 2018-12-07
CN105813998A (zh) 2016-07-27
TW201514120A (zh) 2015-04-16
KR102271837B1 (ko) 2021-07-02
KR20160067916A (ko) 2016-06-14
US20170050878A1 (en) 2017-02-23

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